Stabilized chlorinated paraffin wax and method of producing



awed ay 31,1938 a I 2,119,149

UNITED STATES PATENT-OFFICE STABILIZED CHLORINATED PARAFFIN AND METHOD OF PRODUCING William '1. Bishop, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application April 9, 1935,

' Serial No. 15.505

'15 Claims. (01. zoo-162) This invention relates to stabilized chlorinated paramn wax and the alkaline liquid may be parafiin waxes and to methods for effecting such used in accordance with this invention in any stabilization. amounts and proportions convenient for thor- Chlorinated paramn waxes, as prepared by ough admixture and contact. various known methods, slowly decompose, lib- In order to insure thorough and complete con- '5 erating hydrogen chloride. This characteristic tact between the chlorinated paraffin wax and renders them unfit for many uses for which the alkaline liquid it is desirable to agitate the they would otherwise be well suited. The slow mixture vigorously during-the treatment. The decomposition referred to and the hydrogen chlostabilization treatment may be carried out at ride thereby produced are not to be confused any temperature, but desirably a temperature 10 with the hydrogen chloride present in impure of from about 50 C. to about 100C.,' and prefchlorinated paraffin waxes as taken from the erably of from about 70 C. to about 80 C.,

chlorinating apparatus. This latter hydrogen will be employed. The necessary duration of chloride is a by-product of the chlorination and the treatment cannot be given exactly, for it may be removed by known purification treat- .will vary widely for different products treated ments, as, for example, by passing a stream of and for different alkaline materials. However,

air or carbon dioxide through 'theagitated, a period of from to 6 hours will usually suflice molten chlorinated paraffin wax. The purified for satisfactory stabilization.

chlorinated paraflin wax so produced will never- Where the chlorinated paraffin wax or solutheless, upon standing for a few hours, give off tion thereof and the alkaline liquid are im- 20 appreciable amounts of hydrogen chloride miscible, as will usually be the case, the agitathrough decomposition. tion employed during treatment forms anemul- Now in accordance with this invention it has sion. The stabilized chlorinated paraffin wax been found that chlorinated paraffin wax may may be separated from this emulsion by a vabe stabilized so that its decomposition is greatly 5 riety of methods. For example, it may be re- 25 retarded by being thoroughly washed or admixed covered by distillation of the alkaline liquid or with an alkaline liquid, as, for example, an aqueous phase thereof, by centrifugation or setaqueous solution of sodium hydroxide, sodium tling, and by extraction with a solvent therefor, carbonate, potassium hydroxide, potassium caras, for example, ether, toluene, naphtha, benbonate, calcium hydroxide, sodium bicarbonate, zene, carbon tetrachloride, turpentine, etc. This '30 potassium bicarbonate, ammonia, amines, ete., last method of recovery, being most simple and which is later separated from the chlorinated eflicient, is preferred. paraffin wax. Surprisingly, it has been found in accordance The alkaline liquid employed will preferably, with this invention that the degree of stabilizafor greater ease of separation after treatment, tion effected is, to a large extent, dependent 35 be immiscible with chlorinated paraifin wax. upon the use of particular solvents in the re- Accordingly aqueous or alcoholic solutions are covery of the chlorinated paraffin wax from the the preferred alkaline liquids. Where an aque-- emulsion above described. Thus, when ether or ous solution of an alkali metal or alkaline earth toluene is used as a solvent in recovering chlo- 40 metal hydroxide or carbonate is used as the rinated paraflin wax from this emulsion, a-prod- 40 alkaline liquid, the concentration of the solution uct of much greater stability is obtained than may vary within wide limits, but preferably 1 when the chlorinated paraflin wax is recovered to 20% solutions of alkali metal hydroxides or by using other solvents or in any other manner. carbonates and saturated or nearly saturated The following examples are illustrative of prosolutions of alkali earth metal hydroxides or cedure in accordance with this invention'and 45 carbonates will be used. demonstrate the increase in stability of chlorin- The chlorinated paraffin wax, if liquid, will ated paraflin wax obtained by various procedures: be treated directly with the alkaline liquid. If About 400 g. chlorinated paraflin wax (Sample the chlorinated paraflin wax is a solid, it will A) Conta combined chlorine and free 50 preferably be melted or dissolved in a solvent from uncombined chlorine or hydrogen chloride 50 immiscible with the alkaline liquid to be used, was added to 2 liters of a saturated solution as, for example in aromatic hydrocarbons such of calcium hydroxide, and the mixture was Vi as toluene or benzene, carbon tetrachloride, orously agitated for about eight hours at a. ether, etc., before treatment to insure better temperature of 75-80 C. The emulsion so 65 contact with the alkaline liquid. The chlorinated formed was divided into two portions. One portion was extracted with ether and the ether evaporated for the recovery of the chlorinated paraflln wax. This material was designated Sample A2. The second portion was distilled for the removal of the waterpresent, and the mixture of chlorinated paraflin wax and calcium hydroxide thinned slightly with carbon tetrachloride and filtered. The chlorinated paraffin wax recovered from the filtrate was designated Sample A3. The stability of Samples A2 and A3 compared with each other and with the untreated original Sample A are tabulated below: The stability data are obtained by a test which consisted in heating a l-gram sample of chlorinated paraflln wax in a 6" x A" test tube, with a piece of Congo red test paper %"x suspended by a wire so that the lower edge of the paper is 4%! from the surface of the sample. The wire is held by a cork which tightly closes the test tube. The test tube is then heated in a bath at C., and the time required for the Congo red paper to change color from red to blue at its lower edge recorded as a measure oi! stability oi the sample under test.

It will be noted that Sample A3 which had been subjected to the alkali treatment but not the ether extraction was decidedly more stable than the original sample. Sample'A2, however, which had had the alkali treatment followed by the ether extraction showed a stability test more than four times that of Sample A3. The action oi the ether in improving the stability is obviously very great.

A further portion of chlorinated paraflin wax (Sample A) was treated with calcium hydroxide solution as described above and the emulsion produced divided into two portions. One of these was then extracted with ether, and the other with naphtha for the recovery of the chlorinated paraflin wax. The two samples so obtained were designated A4 and ASrespectively, and comparative data on their stability is tabulated below:

1 5 Description 0! sample Stability Original sample 0 minute. Ether extracted sample (test stopped 6 hours.

before iailure Naphtha extracted sample 92-1 hour.

It will be noted that naphtha does not give the stabilization that ether does. In fact a compari-: son or the stability shown for Sample A5 in this table with that shown for Sample A3 above,

seems to indicate that the naphtha extraction actually lowers the stability. It should be noted, however, that these samples had had separate alkali treatments, which probably account for this difference. It is believed, from a large number of experiments, that the naphtha extraction has no eflect one way or the: other on the stability.

Another 200 g. portion of chlorinated paramn wax (Sample A) was vigorously agitated at 1%? Description of sample Stability A Original sample 0 minute. A6 Sample washed with sodium hydroxide 5 hours.

solution. Duplicate test on sample A6 4% hours.

About 300 g. of a chlorinated paraflin wax (Sample B) containing 40.7% combined chlorine and free from uncombined chlorine and hydrogen chloride was agitated for about 4 hours at 80 C. with 1 liter of saturated calcium hydroxide solution'. The resulting emulsion, after cooling, was,

divided into three equal portions. The portions were extracted with ether, naphtha and toluol, respectively, and the chlorinated paramn wax recovered from each extract and tested for stability. The data obtained are tabulated below:

. sample No, wfil ifid recovered asttiligg mv' Hours B1 Ether 2% Dunlimta 2 Dnnlimta 2% B2 Naphtha 1% Duplicat 1% 3 Toluol 2 2% NaOH washed Stilbilii; Samp recovered from at 100 l0 Duplicate 13 A further portion of chlorinated paraffin wax (Sample B) was similarly treated with a 5% 60 sodium hydroxide solution. Two portions of the resultant emulsion were separately extracted with naphtha and ether, and stability data obtained on the chlorinated paraffin wax recovered, follow: 65

5 N 0H 11 d St h'l't sample r ecoewered fio m at 5 06 B7 Naphtha 70 Dnnlimta 1% Duplicate 1 51 No change a t .51 hours.

200 g. of chlorinated parafiin wax (Sample B) were then similarly treated with a 2% sodium bicarbonate solution. The emulsion produced was separated into two portions, and the portions extracted with ether and naphtha, respectively. The stability tests on the recovered chlorinated paraifln'wax are tabulated below:

2% NsHCO; washed Stabilit Sample recovered from at 100 Minutes B9 Ether l7 Duplicate 20 B10 Nnphi'hn Dnnlimta 7 Chlorinated paramn wax (Sample C) containing 46% combined chlorine was treated with a 5% solution of sodium hydroxide in'thc manner hereinbefore described. The emulsion formed was extracted with ether, and the extract evaporated for recovery of the chlorinated paraflin wax. Stability data are tabulated below:

57 NaOH washed Stabilit Sample i ecovered irom at l00 Home 01 Ether 48 Duplicate 48% of organic bases, as for example, aniline, pyridine,

etc., as is more fully disclosed in an application Serial No. 19,468, filed May 2, 1935 by me jointly with Emil Ott.

It will be understood that the details and examples hereinbefore set forth are illustrative only, I and are in no way in limitation of the invention as herein broadly described and claimed.

What I claim and desire to protect by Letters Patent is:

1. A method for the stabilization of chlorinated paraffln wax whichincludes admixing chlorinated paraflin wax with an alkaline liquid immiscible therewith, extracting the chlorinated paraflln wax from the mixture with a solvent therefor which is substantially immiscible with the alkaline liquid, andrecovering a stabilized chlorinated parafiln wax from the extract.

2. A method for the stabilization of chlorinated paraflin wax which includes admixing chlorinated paraffln wax with an aqueous solution of an alkaline material, extracting the. chlorinated paraffln wax from the mixture with a solvent therefor, which is substantially immiscible with the alkaline liquid, and recovering a stabilized chlorinated paramn'wax from the extract.

3. A method forthe stabilization of chlorinated paraflin wax which includes admixing chlorinated paraffin wax with an aqueous sodium hydroxide solution, extracting the chlorinated paraflin wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinated paraflln wax from the extract.

4. A method for the stabilization of chlorinated paraiiln wax which includes admixing chlorinated paraffin wax with an aqueous calcium hydroxide solution, extracting the chlorinated paramn wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinatedparaflln wax from the extract.

5. A method for the stabilization of chlorinated paraiiin wax which includes admixing chlorinated paraffin wax with an alkaline liquid immiscible therewith, extracting the chlorinated paraffln wax from the mixture with ether, and

recovering a stabilized chlorinated paraffin wax from the extract.

6. A method for the stabilization of chlorinated paraflin wax which includes admixing chlorinated paraflln wax with an alkaline liquid immiscible therewith, extracting the chlorinated paraflin wax from the mixture with toluol, and recovering a'stabilized chlorinated paraffin wax from the extract.

7. A method for the stabilization of chlorinated paraifin wax which includes admixing chlorinated paraflin wax with an alkaline liquid immiscible therewith, agitating the mixture, extracting the chlorinated paraflln wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinated paramn wax from the extract.

8. A method for the stabilization of chlorinated paraffln wax which includes admixing chlorinated parafiln wax with an alkaline liquid immiscible therewith, agitatingthe mixture at a temperature of from about 50 C. to about 100 C., extracting the chlorinated paraffln wax from the a mixture with a solvent therefor selected from the 1 group consisting of ether and toluol, and recovering a stabilized chlorinated paraffin wax from the extract. 9. A method for the stabilization of chlorinated paraflin waxwhich includes admixing chlorinated paramn wax with an alkaline liquid immiscible therewith, agitating the mixture for L from about to about 6 hours at a temperature of from about 50 C. to about 100 C., extracting the chlorinated paraflln wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinated parailin wax from the extract.

10. A highly stabilized chlorinated paraflin wax characterized by the fact that it possesses very little tendency to decompose with evolution of hydrogen chloride and comprising a chlorinated paraflln wax which has been admixed with an alkaline liquid and recovered from such mixture by extraction with a solvent therefor selected from the group consisting of ether and toluol.

11. A method for the stabilization of chlorinated paraffin wax which includes admixing chlorinated paraflln wax with an alkaline liquid immiscible therewith, extracting the chlorinated paraflin wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinated paramn wax from the extract.

12. A method for the stabilization of chlorinated paraflin wax which includes admixing chlorinated paramn wax with an aqueous solution of an alkaline material, extracting the chlorinated paraflin wax from the mixture with a solvent therefor selected from the group consisting of ether and toluol, and recovering a stabilized chlorinated parafiln wax from the extract.

13. A highly stabilized chlorinated paraflln wax characterized by having a stability to evolution of hydrogen chloride of not less than about six hours when measured as the time required for the lower edge of a x piece of Congo red test vpaper to turn from red to blue in the presence of moisture when suspended 4%" from the surface .of a 1 gram sample of chlorinated paraflln in a closed 6" x test tube when heated in a bath at 100 C.

1-1. A method m the stabilization of chlorin J ated paraflln wax which includes admixing chlorinated paramn wax with an aqueous sodium hy- -droxide solution, extracting the chlorinated WILLIAM: BiSHOP. 

